CN115216017A - Preparation method and application of alkoxy polysilazane - Google Patents
Preparation method and application of alkoxy polysilazane Download PDFInfo
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Abstract
The invention discloses a preparation method and application of alkoxy polysilazane, wherein the method comprises the following steps: (1) At least one of chlorosilane shown in formula 1 and at least one of alkoxy silane shown in formula 2 are mixed according to the proportion under inert atmosphere for reaction, and a byproduct R is removed 2 R 3 R 4 SiCl to prepare a precursor; (2) And (2) carrying out ammonolysis reaction on the precursor prepared in the step (1) to prepare alkoxy polysilazane. The invention quantitatively forms a precursor by controlling the proportion of chlorosilane shown in a formula 1 and alkoxy silane shown in a formula 2, thereby accurately controlling the structure and the composition of alkoxy polysilazane formed after the precursor is aminolyzed.
Description
Technical Field
The invention relates to a simple and efficient preparation method of alkoxy polysilazane and preparation of SiO x N y The invention relates to an application of ceramics, belonging to the field of polymer synthesis.
Background
Alkoxy polysilazanes are a high molecular material with a main chain mainly comprising Si-N bonds and at least one alkoxy on a side chain, are converted into Si-O-N inorganic materials with excellent temperature resistance, oxidation resistance and dielectric property under high temperature, light or humid air, and are widely used for preparing ceramic matrix composite materials, high temperature resistant adhesives, coatings, fibers, films and the like. JP10245435 discloses a catalyst containing a baseWith RSiCl in the case of the reagent 3 Reacting with alcohol to generate alkoxy chlorosilane, and then reacting with NH 3 Or reacting organic amine to generate alkoxy silazane; SU922110A1 discloses the use of tetrachlorosilane and tetramethoxy (or tetraethoxy) silane in the presence of a catalyst by exchange reaction to form alkoxychlorosilanes which are then aminolyzed to form alkoxysilazalazanes. Yuji Iwamoto uses SiCl 4 Reacting with monohydric alcohol to generate alkoxy chlorosilane, and performing ammonolysis on the separated and purified alkoxy trichlorosilane at-78 ℃ to generate alkoxy polysilazane with a branched structure. In the method, both chlorosilane and alcohol are adopted to react or chlorosilane and alkoxy silane are adopted to react, the generated alkoxy chlorosilane is a mixture, and the composition and the structure of alkoxy silazane formed by aminolysis are difficult to accurately control.
Disclosure of Invention
In order to improve the technical problem, the invention provides a simple method for preparing alkoxy polysilazane with a controllable structure and application thereof in SiO x N y Application in the preparation of ceramics.
The technical scheme of the invention is as follows:
a method of preparing an alkoxy polysilazane, the method comprising the steps of:
(1) At least one of chlorosilane shown in formula 1 and at least one of alkoxy silane shown in formula 2 are mixed according to the proportion under inert atmosphere for reaction, and a byproduct R is removed 2 R 3 R 4 SiCl to prepare a precursor;
R m SiCl n (formula 1)
In formula 1, R is the same or different and is independently selected from H or Cl, m + n =4, m is 0, 1 or 2;
R 2 R 3 R 4 SiOR 1 (formula 2)
In the formula 2, R 1 Is a hydrocarbyl group; r 2 、R 3 、R 4 Are the same or different and are each independently selected from C 1-10 One of alkyl groups;
R 2 R 3 R 4 in SiCl, R 2 、R 3 、R 4 Is as defined in formula 2;
(2) And (2) carrying out ammonolysis reaction on the precursor prepared in the step (1) to prepare alkoxy polysilazane.
Illustratively, R 1 Is C 1-6 Alkyl or C 2-6 An alkenyl group.
For example, the C 1-6 The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a tert-butyl group, a hexyl group 1-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl 2-methyl amyl, 1-methyl amyl, 2-ethyl butyl, 1-ethyl butyl, 3-two methyl butyl, 2-two methyl butyl, 1-two methyl butyl, 2, 3-two methyl butyl, 1, 3-two methyl butyl or 1, 2-two methyl butyl or their isomers and at least one;
said C is 2-6 Alkenyl may be vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, at least one of (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl and the like.
Preferably, said R is 1 Is ethyl or isoPropyl or n-hexyl; the R is 2 、R 3 、R 4 Are all methyl.
The chlorosilane represented by formula 1 is a commercially available chlorosilane.
Illustratively, the chlorosilane is selected from, for example, siCl 4 、H 2 SiCl 2 、HSiCl 3 、SiCl 4 And H 2 SiCl 2 Mixture of (1), siCl 4 And HSiCl 3 Mixture of (1), H 2 SiCl 2 And HSiCl 3 A mixture of (A) or (H) 2 SiCl 2 With HSiCl 3 And SiCl 4 The mixture of the three components.
In step (1), the molar ratio of at least one chlorosilane represented by formula 1 to at least one alkoxysilane represented by formula 2 is 1. For example, the ratio can be 1.
In the step (1), the alkoxy silane is added into the chlorosilane in a dropwise manner.
Exemplarily, the step (1) is specifically: under inert atmosphere, at least one of alkoxy silane shown in a formula 2 is dripped into at least one of chlorosilane shown in a formula 1 according to the proportion, the system temperature is kept between 10 ℃ below zero and 25 ℃, the dripping and the stirring are carried out simultaneously, after the dripping is finished, the reaction is continued, and a byproduct R is removed 2 R 3 R 4 SiCl to prepare a precursor.
In the step (1), the by-product R is removed under the vacuum condition of 5-25 ℃ and 10-500 Pa 2 R 3 R 4 SiCl。
In the step (1), the by-product R is removed 2 R 3 R 4 The SiCl time is 0.1-4 h. For example, it may be 0.1, 1h, 1.5h, 2h, 2.5h, 3h, 4h.
In the step (1), after the dropwise addition of at least one of the alkoxysilanes represented by the formula 2 is completed, the reaction is continued for 0.5 to 48 hours, preferably 2 to 24 hours.
In step (1), the inert atmosphere includes, but is not limited to, a nitrogen atmosphere or an argon atmosphere.
In the step (1), the dropping speed of the alkoxy silane is 2ml/min to 500ml/min, preferably 2ml/min to 100ml/min. For example, the concentration may be 2ml/min, 10ml/min, 30ml/min, 50ml/min, 80ml/min, 100ml/min, 200ml/min, 300ml/min, 400ml/min, or 500ml/min.
In the step (1), the chlorosilane can be dissolved in a solvent, and then the alkoxysilane is added dropwise.
In the step (1), the precursor is selected from at least one of compounds having a structure represented by formula 3:
R m Si(OR 1 ) x Cl y (formula 3)
In formula 3, m, R and R 1 Having the above meaning, x is an integer greater than 0, y is 0 or a positive integer and m + x + y =4 is satisfied.
Illustratively, when the chlorosilane of formula 1 is selected from SiCl 4 The alkoxysilane represented by the formula 2 is selected from Me 3 SiOC 2 H 5 And when the feeding molar ratio of the two is 1.
Exemplarily, the step (2) is specifically: and (2) adding a solvent into the precursor prepared in the step (1), introducing ammonia gas, and carrying out ammonolysis reaction to prepare alkoxy polysilazane.
In the step (2), the solvent comprises C 5-10 Alkanes, ethers, tetrahydrofuran, aromatics, acetone, and the like; said C is 5-10 The alkane may be, for example, pentane, n-hexane, heptane, octane, nonane, decane, etc.; the ethers include, but are not limited to, petroleum ether, diethylene glycol dimethyl ether; the aromatic compound may be, for example, toluene, xylene.
And (3) in the step (2), after ammonia gas is introduced, stopping adding the ammonia gas until the pH value of the system is 9-10.
In the step (2), when ammonia gas is introduced, the system temperature is-10 ℃ to 25 ℃. For example, the temperature may be-10 ℃,0 ℃, 5 ℃,10 ℃, 15 ℃, 18 ℃, 20 ℃ and 25 ℃.
In the step (2), post-treatment is carried out on the alkoxy polysilazane, and the post-treatment step is as follows: separating the solid-liquid mixture after ammonolysis, collecting the liquid, and concentrating under 10-500 Pa vacuum to obtain the purified alkoxy polysilazane.
In the step (2), the concentration temperature is 10-80 ℃. Illustratively, the temperature of concentration is 10, 15, 20, 25, 30, 40, 45, 50, 60, 62, 65, 70, 75, 78, or 80 ℃.
According to the invention, the preparation method of the alkoxy polysilazane specifically comprises the following steps:
(1) Under inert atmosphere, adding at least one of chlorosilane shown in formula 1 into a three-neck flask which is provided with a constant-pressure dropping funnel and is mechanically stirred, adding at least one of alkoxysilane shown in formula 2 into the dropping funnel, dropwise adding the alkoxysilane into the chlorosilane, keeping the temperature of the system between minus 10 and 25 ℃, dropwise adding while stirring, and continuing to react after the dropwise adding is finished; after the reaction is finished, the reaction product is treated for 10min to 4h under the vacuum condition of 5 to 25 ℃ and 10 to 500Pa, and a by-product R after chlorosilane alcoholysis is removed 2 R 3 R 4 SiCl to prepare a precursor shown in a formula 3;
(2) Adding a solvent into the precursor shown in the formula 3 in the step (1) in an inert atmosphere, uniformly mixing, keeping the temperature of the system at-10-25 ℃, introducing dried ammonia gas into the system for aminolysis, and stirring while aminolysis is carried out until the pH value of the system reaches 9-10; separating the solid-liquid mixture after ammonolysis, collecting the liquid, and concentrating under 10-500 Pa vacuum to obtain the alkoxy polysilazane.
According to the invention, the by-product R separated off in step (1) 2 R 3 R 4 SiCl can react with alcohol to form alkoxysilane represented by formula 2, and the alkoxysilane can be recycled. The alcohol may be R 1 OH，R 1 The definition of (1) is as before; illustratively, it may be at least one of methanol, ethanol, isopropanol, butanol, etc.
According to the present invention, the alkoxy polysilazanes prepared according to the present invention may further comprise a hetero element including, but not limited to, at least one of Al, B, ti, zr, hf, etc.
According to the present invention, the hetero element in the alkoxy polysilazane is introduced by introducing a chloride containing the hetero element into a mixture of at least one of the chlorosilanes represented by formula 1 and at least one of the alkoxysilanes represented by formula 2 in the above step (1) to effect a reaction.
Illustratively, the molar ratio of the chloride containing the hetero element to at least one of the chlorosilanes represented by formula 1 is 0.1 to 10.
Illustratively, the method for preparing alkoxy polysilazanes containing hetero elements comprises the following steps:
under the protection of inert gas, uniformly mixing chloride containing a hetero element, at least one chlorosilane shown in a formula 1 and at least one alkoxysilane shown in a formula 2 according to a ratio, and reacting at-10-25 ℃; after the reaction is finished, processing for 10min to 4h under the vacuum condition of 5 to 25 ℃ and 10 to 500Pa, and removing by-products; introduction of NH 3 Reacting at-10-25 ℃ until the pH value of the system is 9-10, and stopping introducing NH 3 Preparing alkoxy polysilazane containing hetero elements.
The invention also provides alkoxy polysilazane, which is prepared by the method.
In particular, the alkoxy polysilazanes can be solid, liquid or highly viscous.
The invention also provides application of the alkoxy polysilazane to preparation of ceramics, fibers, prepregs, coatings (such as hot melt coatings), adhesives and the like.
Preferably, it is applied to the preparation of SiO x N y Ceramic of which 0<x is less than or equal to 2, y is more than or equal to 0 and less than or equal to 1.x or y can be a decimal or an integer, for example x is 0.5, 0.7, 0.8, 1 or 2; y is 0, 0.4, 0.6, 0.8 or 1.
The present invention also provides a method for preparing a ceramic, the method comprising the steps of:
a) Preparing alkoxy polysilazane by the above-mentioned method;
b) Reacting the alkoxy polysilazane of step a) in at least one of humid air, ammonia water atmosphere, light or heat to prepare the ceramic.
Illustratively, the ceramic is SiO x N y Ceramics ofMiddle, 0<x≤2，0≤y≤1。
In the present invention, the moisture content in the humid air is 15% to 90%, preferably 30% to 80%.
In the invention, the concentration of ammonia water in the ammonia water atmosphere is 1-80%, preferably 10-40%. Illustratively, the concentration of ammonia is 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 65%, 70%, 75%, 80%.
In the present invention, the light irradiation condition refers to at least one of ultraviolet, x-ray and gamma-ray.
In the present invention, the heating condition is to heat the alkoxy polysilazane at 50 to 800 ℃, preferably 150 to 600 ℃ in an atmosphere of air, nitrogen, argon or ammonia. Illustratively, the heating temperature is 50, 80, 100, 150, 200, 250, 300, 400, 500, 600, 650, 700, 750, or 800 ℃.
In the invention, the reaction time is 2 min-24 h.
Advantageous effects
Firstly, at least one of the chlorosilanes shown in the formula 1 and at least one of the alkoxysilanes shown in the formula 2 are used for reaction to form the alkoxy chlorosilane, the reaction conditions are mild, and a catalyst is not required. By controlling the ratio of at least one chlorosilane shown in the formula 1 to at least one alkoxysilane shown in the formula 2, a precursor of at least one compound shown in the formula 3 is quantitatively formed, and the structure and the composition of the alkoxy polysilazane formed after ammonolysis of the precursor are precisely controlled.
Second, a byproduct R separated during the reaction 2 R 3 R 4 SiCl can react with corresponding alcohol to form alkoxy silane shown in the formula 2 for reuse, so that resources are saved, and production cost is reduced.
Third, the present invention can prepare not only alkoxy polysilazanes but also alkoxy polysilazanes containing hetero elements including but not limited to Al, B, ti, zr, hf.
Drawings
FIG. 1 shows the preparation of ethoxytrichlorosilane in example 1 29 A SiNMR image;
FIG. 2 is a schematic representation of the ethoxylated polysilazane of example 3 29 A SiNMR image;
FIG. 3 is SiO in example 8 x Is detected.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Preparing a precursor A:
s1: under the protection of inert atmosphere, 0.1mol of silicon tetrachloride is added into a three-neck flask which is provided with a constant-pressure dropping funnel and is mechanically stirred by an injector, the temperature of the system is kept at-10 ℃, and 0.1mol of Me is added into the dropping funnel 3 SiOEt is dripped into the chlorosilane solution at the speed of 2ml/min while stirring, and the reaction is continued for 24 hours after the dripping is finished.
S2: after the reaction is finished, the temperature of the system is controlled at 5 ℃, and the reaction product is treated for 2 hours under the vacuum condition of 10Pa to remove the by-product Me after chlorosilane alcoholysis 3 SiCl, and preparing a precursor A, namely ethoxy trichlorosilane.
For precursor A 29 Characterization by SiNMR, etOSiCl 3 The silicon spectral position was-37.8 ppm (see FIG. 1), demonstrating that precursor A was prepared as ethoxytrichlorosilane.
Example 2
Preparing a precursor B:
s1: under the protection of inert atmosphere, 0.1mol of silicon tetrachloride is added into a three-neck flask which is provided with a constant-pressure dropping funnel and is mechanically stirred by an injector, the temperature of the system is kept at-10 ℃, and 0.12mol of Me is added into the dropping funnel 3 SiOEt, and is dripped into the chlorosilane solution at the speed of 10ml/min while stirring, and the SiOEt is dripped into the chlorosilane solutionAnd 24h after the completion.
S2: after the reaction is finished, the temperature of the system is controlled at 5 ℃, and the reaction product is treated for 2 hours under the vacuum condition of 10Pa to remove the by-product Me after chlorosilane alcoholysis 3 SiCl to prepare a precursor B, namely EtOSiCl 3 And (EtO) 2 SiCl 2 Is 4.
Using the precursor B 29 SiNMR characterization, with silicon spectral positions of-37.8 ppm and-56.4 ppm, respectively, indicating that the product is EtOSiCl 3 And (EtO) 2 SiCl 2 None (EtO) 3 SiCl is generated, and the molar ratio of SiCl to SiCl is 4:1, according with the batch charging ratio.
Example 3
Preparation of solid ethoxylated polysilazane:
adding the precursor A obtained in the example 1 into a three-neck flask, adding 50ml of toluene solvent, uniformly mixing under the condition of mechanical stirring, controlling the system temperature at 5 ℃, introducing dry ammonia gas for ammonolysis, stopping introducing the ammonia gas when the pH is measured to be 9, filtering and separating a product and a byproduct ammonium chloride, collecting a separated solution, and removing toluene under the vacuum condition of 80 ℃ and 100Pa to obtain solid ethoxy polysilazane, wherein a silicon spectrogram of the solid ethoxy polysilazane is shown in figure 2.
Example 4
Preparation of solid ethoxylated polysilazane:
adding the precursor B obtained in the embodiment 2 into a three-neck flask, adding 50ml of petroleum ether (60-90 ℃) solvent, uniformly mixing under the condition of mechanical stirring, controlling the system temperature at 25 ℃, introducing dry ammonia gas for ammonolysis, stopping introducing the ammonia gas when the pH value is measured to be 10, filtering and separating the product and a byproduct ammonium chloride, collecting the separated solution, and removing the petroleum ether under the vacuum condition of 10 ℃ and 500Pa to obtain the solid ethoxy polysilazane.
Example 5
Preparation of liquid ethoxypolysilazane:
s1: under the protection of inert atmosphere, 0.1mol of silicon tetrachloride is added into a three-neck flask which is provided with a constant-pressure dropping funnel and is mechanically stirred by an injector, the temperature of the system is kept at-10 ℃, and 0.15m of silicon tetrachloride is added into the dropping funnelol Me 3 SiOEt is dripped into the chlorosilane solution at the speed of 10ml/min while stirring, and the reaction is continued for 24 hours after the dripping is finished.
S2: after the reaction is finished, the temperature of the system is controlled at 5 ℃, and the reaction product is treated for 2 hours under the vacuum condition of 10Pa to remove the by-product Me after chlorosilane alcoholysis 3 SiCl to prepare a precursor C, wherein the precursor C is EtOSiCl 3 And (EtO) 2 SiCl 2 A mixture of (a); etOSiCl 3 And (EtO) 2 SiCl 2 1 is 1.
S3: adding 100ml of n-hexane into the system, uniformly mixing under the condition of mechanical stirring, controlling the temperature of the system at 5 ℃, introducing dry ammonia gas for aminolysis, stopping introducing ammonia when the pH is measured to be 9, filtering and separating the product and a by-product ammonium chloride, collecting the separated solution, and removing the n-hexane under the vacuum condition of 20 ℃ and 100Pa to obtain the liquid ethoxy polysilazane.
Example 6
Preparing high-viscosity-state hexyloxy polysilazane:
s1: under the protection of inert atmosphere, 0.1mol of silicon tetrachloride and 0.01mol of dihydrodichlorosilane are added into a three-mouth bottle which is provided with a constant-pressure dropping funnel and is mechanically stirred by an injector, the temperature of the system is kept at 0 ℃, and 0.1mol of n-Hex-OSiMe is added into the dropping funnel 3 And dropwise adding the mixture into a chlorosilane solution at the speed of 100ml/min while stirring, and continuously reacting for 10 hours after the dropwise adding is finished.
S2: after the reaction is finished, the temperature of the system is controlled at 5 ℃, and the reaction product is treated for 2 hours under the vacuum condition of 10Pa to remove the by-product Me after chlorosilane alcoholysis 3 SiCl, and preparing a precursor D, wherein the precursor D is a mixture of n-hexyloxy trichlorosilane and n-hexyloxy (dihydro) monochlorosilane.
S3: adding 60 ml of tetrahydrofuran solvent into a three-necked bottle of the precursor D, uniformly mixing under the condition of mechanical stirring, controlling the system temperature at 10 ℃, introducing dry ammonia gas for ammonolysis, stopping introducing ammonia when the pH value is 10, filtering and separating a product and a by-product ammonium chloride, collecting a separated solution, and removing tetrahydrofuran under the vacuum conditions of 40 ℃ and 50Pa to obtain the high-viscosity hexyloxy polysilazane.
Example 7
Preparation of liquid isopropoxypolysilazane:
s1: under the protection of inert atmosphere, 0.1mol of silicon tetrachloride is added into a three-neck flask which is provided with a constant-pressure dropping funnel and is mechanically stirred by an injector, the temperature of the system is kept at-10 ℃, and 0.15mol of iPrOSiMe is added into the dropping funnel 3 And dropwise adding the mixture into a chlorosilane solution at the speed of 10ml/min while stirring, and continuing to react for 24 hours after the dropwise adding is finished.
S2: after the reaction is finished, the temperature of the system is controlled at 5 ℃, and the reaction product is treated for 2 hours under the vacuum condition of 10Pa to remove the by-product Me after chlorosilane alcoholysis 3 SiCl, and preparing a precursor E, wherein the precursor E is a mixture of isopropoxytrichlorosilane and diisopropoxydichlorosilane.
S2: adding 100ml of diethylene glycol dimethyl ether into the precursor E system, uniformly mixing under the condition of mechanical stirring, controlling the temperature of the system at 5 ℃, introducing dry ammonia gas for ammonolysis, stopping introducing ammonia when the pH is measured to be 9, filtering and separating a product and a by-product ammonium chloride, collecting a separated solution, and removing the diethylene glycol dimethyl ether under the vacuum condition of 80 ℃ and 10Pa to obtain liquid isopropoxy polysilazane.
Example 8
Preparation of SiO x Ceramics:
the solid ethoxy polysilazane obtained in example 3 was formulated into a 10% n-butyl ether solvent, coated on a stainless steel sheet by dip coating (spray coating or spin coating), and then placed in a constant temperature and humidity chamber at 25 ℃ and a humidity of 80% to treat for 10 hours, thereby obtaining a stainless steel sheet with a coating. The coating is characterized by infrared, the ethoxy polysilazane is completely converted into SiOx, and x is 1.7-2.0. SiO as shown x The infrared spectrum of (A) is shown in FIG. 3.
Example 9
Preparation of SiO x Ceramic:
the solid ethoxy polysilazane obtained in example 3 was formulated into a 10% n-butyl ether solvent, coated on a stainless steel sheet by dip-coating (spray coating or spin coating), and then placed in a constant temperature and humidity chamber with 50 ℃, 30% ammonia concentration, and 60% water content in humid air, and after 6 hours of treatment, represented by infrared, the ethoxy polysilazane was completely converted into SiOx, with x being 1.7 to 2.0.
Example 10
Preparation of SiO x Ceramic:
the solid ethoxy polysilazane obtained in example 3 was placed in a tube furnace and heat-preserved at 800 ℃ for 2 hours at a heating and cooling rate of 5 ℃/min in a nitrogen atmosphere, the ceramic yield was 50%, and the carbon content of the product was less than 2% of that of SiO x N y The ceramic of (1) wherein x is 0.8 to 1.2 and y is 0.4 to 0.6.
Example 11
Preparation of SiO x Ceramics:
the solid ethoxy polysilazane obtained in example 3 was formulated into 10% n-butyl ether solvent, coated on a stainless steel sheet by dip coating (spray coating or spin coating), and the stainless steel sheet was treated under ultraviolet irradiation for 2 minutes, and the obtained cured product was characterized by infrared, and the ethoxy polysilazane was completely converted into SiOx, with x being 1.7 to 2.0.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of preparing an alkoxy polysilazane, comprising the steps of:
(1) At least one of chlorosilane shown in a formula 1 and at least one of alkoxy silane shown in a formula 2 are mixed according to a ratio in an inert atmosphere for reaction, and a byproduct R is removed 2 R 3 R 4 SiCl to prepare a precursor;
R m SiCl n (formula 1)
In formula 1, R is the same or different and is independently selected from H or Cl, m + n =4, m is 0, 1 or 2;
R 2 R 3 R 4 SiOR 1 (formula 2)
In the formula 2, R 1 Is a hydrocarbyl group; r 2 、R 3 、R 4 Are the same or different and are each independently selected from C 1-10 One of alkyl groups;
R 2 R 3 R 4 in SiCl, R 2 、R 3 、R 4 Is as defined in formula 2;
(2) And (2) carrying out ammonolysis reaction on the precursor prepared in the step (1) to prepare alkoxy polysilazane.
2. The method of claim 1, wherein R is 1 Is C 1-6 Alkyl or C 2-6 An alkenyl group.
Preferably, said R is 1 Is ethyl, isopropyl or n-hexyl; said R is 2 、R 3 、R 4 Are all methyl.
3. The method according to any one of claims 1-2, wherein the chlorosilane of formula 1 is selected from SiCl 4 、H 2 SiCl 2 、HSiCl 3 、SiCl 4 And H 2 SiCl 2 Mixture of (1), siCl 4 And HSiCl 3 Mixture of (1), H 2 SiCl 2 And HSiCl 3 A mixture of (A) or (H) 2 SiCl 2 With HSiCl 3 And SiCl 4 The mixture of the three components.
Preferably, in step (1), the molar ratio of at least one chlorosilane represented by formula 1 to at least one alkoxysilane represented by formula 2 is from 1 to 0.8.
4. The production method according to any one of claims 1 to 3, wherein in the step (2), after the introduction of the ammonia gas, the addition of the ammonia gas is stopped until the pH of the system is 9 to 10.
Preferably, in the step (2), when ammonia gas is introduced, the system temperature is-10 ℃ to 25 ℃.
5. According toThe process according to any one of claims 1 to 4, wherein R is a by-product separated in step (1) 2 R 3 R 4 SiCl reacts with alcohol to form alkoxysilane represented by formula 2, which is recycled.
Preferably, the alcohol may be R 1 OH，R 1 The definition of (1) is as before; illustratively, the alcohol is at least one of methanol, ethanol, isopropanol, butanol.
6. The method of any one of claims 1-5, wherein the alkoxy polysilazane prepared further comprises a hetero element including, but not limited to, at least one of Al, B, ti, zr, hf.
7. The method according to claim 6, wherein the hetero element in the alkoxypolysilazane is introduced by introducing a chloride containing a hetero element into a mixture of at least one of the chlorosilanes represented by the above-mentioned formula 1 and at least one of the alkoxysilanes represented by the above-mentioned formula 2 to perform a reaction.
Preferably, the molar ratio of the chloride containing the hetero element to at least one of the chlorosilanes represented by formula 1 is 0.1 to 10.
8. An alkoxy polysilazane, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. Use of an alkoxy polysilazane according to claim 8 for the production of ceramics, fibers, prepregs, coatings (e.g., hot melt coatings), adhesives.
Preferably, it is applied to the preparation of SiO x N y Ceramic of which 0<x≤2，0≤y≤1。
10. A method of making a ceramic, comprising the steps of:
a) Preparing an alkoxy polysilazane by the method of any one of claims 1 to 7;
b) Reacting the alkoxy polysilazane of step a) in at least one of humid air, ammonia atmosphere, light or heat to prepare the ceramic.
Preferably, the ceramic is SiO x N y Ceramic of which 0<x≤2，0≤y≤1。
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